The present invention relates to hydrophobically modified polycarboxylate polymers and a method for promoting soil release from fabrics, particularly cotton and cotton-containing fabrics, by contacting the fabrics with compositions comprising said polymers.
Soil on laundry falls into two general categories; either i) clay soil comprising particles which generally comprise negatively charged layers of aluminosilicates and positively charged cations, for example Ca++, which are positioned between the aluminosilicate layers and hold them together; or ii) oil- or grease borne soils which are typically caused by spills of frying oil, grease, tomato or spaghetti sauce, human body sweat (sebum), and non-saponifiable oil stains such as used motor oil or petroleum oils. Oil-borne stains can usually be removed by dry cleaning but this is expensive. Previously, such oily soil would have been removed using very hot (typically 60-90xc2x0 C.) wash conditions, however, the current trend is to save energy and use much lower washing temperatures in the region of 15-50xc2x0 C.; unfortunately, however, oily soil is not easily removed at this temperature.
Very many soil release agents are known in the art for use in domestic and industrial fabric treatment processes such as laundering, stain guarding, fabric softening etc. For example, polyesters of terephthalic and other aromatic dicarboxylic acids having soil release properties are widely disclosed in the art, such as the so-called PET/POET polymers (polyethylene terephthalate/polyoxyethylene terephthalate), which have been known for over 20 years and the PET/PEG (polyethylene terephthalate/polyethylene glycol) polymers which are taught in, for example, Canadian Patent No. 1,100,262, U.S. Pat. No. 3,557,039 and United Kingdom Patent No. GB 1,467,098.
These PET/POET and PET/PEG polymers are known to be helpful to promote the release of oily soil particularly from synthetic fibres such as polyester. It is believed that their effectiveness is due to the affinity resulting from the similarity between the structure of the PET/POET and PET/PEG polymers and the polyester fibres. Over the last few years, the backbone and side-chains in the PET/POET and PET/PEG polymers have been modified to achieve a range of cost effective polyester soil release additives which can be formulated into liquid and solid (granular) detergents. The main drawback with these materials, however, is that they offer little or no benefit on cotton and cotton blend fabrics; a much larger quantity of polymer is required before any soil release effects are observed and the PET/POET materials, in particular, have low water solubility which makes them difficult to use.
Attempts have been made to use the same approach, that is, to find soil release agents which mimic the structure of cotton and cotton-blend fabrics which will give enhanced soil release on cotton/cotton-blend fabrics. For example, United Kingdom Patent GB 1,314,897 discloses hydroxypropylmethyl cellulose laundry aids for cotton fibre; U.S. Pat. No. 5,049,302 describes a detergent composition having soil release properties comprising an anionic surfactant, a hydrotrope, a graft copolymer of polyalkylene oxide and an ester monomer and a nonionic cellulosic agent for use on cotton and cotton-blend fabrics. Others have suggested permanently modifying the chemical structure of cotton fibres by reacting the substrate with a polysaccharide polymer backbone, for example, U.S. Pat. No. 3,897,026 discloses materials having improved soil release and stain resistance properties obtained by reacting the hydroxyl moieties of the cotton fibres with an ethylene/maleic anhydride co-polymer.
However, despite the extensive research activity in this field, there remains a need for a soil release additive which has superior soil release properties, especially oil- and grease borne soil, and which is highly effective on natural fabrics such as cotton, and cotton-blend fabrics at low temperatures under domestic laundry conditions. Accordingly, the present invention provides polymer of Formula 1: 
wherein:
A is a polymerized residue of a monomer selected from one or more C3-C8 monoethylenically unsaturated carboxylic acids;
B is a polymerized residue of a monomer selected from one or more C3-C60 alkyl(meth)acrylates, ethoxylated C1-C24 alkyl(meth)acrylates, and poly(alkylene glycol)(meth)acrylates, alkyl or aromatic ethers of poly(alkylene glycol) and the corresponding maleate mono and di-esters thereof;
C is a polymerized residue of a monomer selected from one or more ethylenically unsaturated monomers which are copolymerisable with the monomers in A and B;
A, B and C residues are randomly arranged in said polymer;
S and T are end groups;
m is the total number of A residues and is from 0 to 500;
n is the total number of B residues and is  greater than 0;
p is the total number of C residues and is from 0 to 500;
the sum of m and p is at least 1;
q is from 0 to 100; and
D is a polymerized residue of a monomer selected from poly(alkylene)oxide or alkylene oxide monomers
E is selected from C1-C50 alkyl groups and C6-C50 aromatic groups.
X is a functional group.
The term xe2x80x9cA, B and C residues are randomly arranged in said polymerxe2x80x9d means that the residue adjacent the end group S may be either an A, B or C residue, that the residue adjacent the residue adjacent the end group S may be either an A, B or C residue, and so on.
Preferably, the polymer of Formula 1 is formed by copolymerizing two or more monomers A, B and C wherein:
i) monomer A is selected from one or more monoethylenically unsaturated C3-C8 monoethylenically unsaturated carboxylic acid moieties;
ii) monomer B is selected from one or more C3-C60 alkyl(meth)acrylates, ethoxylated C1-C24 alkyl(meth)acrylates, poly(alkylene glycol)(meth)acrylates, alkyl or aromatic ethers of poly(alkylene glycol) and the corresponding maleate mono and di-esters thereof;
iii) monomer C is selected from one or more ethylenically unsaturated monomers which are copolymerisable with monomers A and B;
S and T are end groups;
m is between 0 and 500;
n is  greater than 0;
p is between 0 and 500;
q is from 0-100;
D is selected from poly(alkylene)oxide or alkylene oxide monomer units; and
E is selected from C1 to C50 alkyl and C6 to C50 aromatic groups
X is a functional group.
The present invention also provides a method of promoting the release of oily soil from fabric, comprising contacting the fabric with at least one polymer comprising: 
formed by copolymerising two or more monomers A, B and C wherein:
i) monomer A is selected from one or more monoethylenically unsaturated C3-C8 monoethylenically unsaturated carboxylic acid moieties;
ii) monomer B is selected from one or more C3-C60 alkyl(meth)acrylates, ethoxylated C1-C24 alkyl(meth)acrylates, and poly(alkylene glycol)(meth)acrylates, alkyl or aromatic ethers of poly(alkylene glycol) and the corresponding maleate mono and di-esters thereof;
monomer C is selected from one or more ethylenically unsaturated monomers which are copolymerisable with monomers A and B;
S and T are end groups;
m is between 0 and 500;
n is  greater than 0;
p is between 0 and 500;
q is from 0-100; and
D is selected from poly(alkylene)oxide or alkylene oxide monomer units.
E is selected from C1-C50 alkyl and aromatic groups.
X is a functional group.
Preferably, the molecular weight of the backbone, as measured on the polymer product after exhaustive hydrolysis, comprising polymerizedunits of A, B and C, is at least 500 and may be up to 500,000. Backbone molecular weights of from 500 to 150,000 are especially preferred.
The value m is preferably between 0 and 500. The ratio of m+p:n may be 100:1, preferably 50:1 and particularly preferred is a ratio of between 10:1 to 1:1.
Monomer A, may be selected from C3-C8 monoethylenically unsaturated carboxylic acid moieties. Suitable carboxylic acids include monoethylenically unsaturated monocarboxylic acids and monoethylenically unsaturated dicarboxylic acids. For example, monoethylenically unsaturated carboxylic acids include acrylic acid (AA), methacrylic acid (MAA), alpha-ethacrylic acid, xcex2,xcex2-dimethylacrylic acid, methylenemalonic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid (MAL), maleic anhydride (MALAN), fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and alkali and metal salts thereof Preferably, the monoethylenically unsaturated carboxylic acid is one or more of acrylic, methacrylic or maleic acid. C3-C6 monoethylenically unsaturated carboxylic acids are especially preferred.
Monomer B is preferably selected from one or more of C12-C20 alkyl(meth)acrylates, ethoxylated C12-C20 alkyl(meth)acrylates, poly(C2-C3 alkyleneglycol)(meth)acrylates, alkyl or aromatic ethers of poly(C2-C3 alkylene glycol)(meth)acrylates and the corresponding maleate mono and di-esters thereof. Suitable (meth)acrylates include propyl and higher linear and branched alkyl esters of (meth)acrylic acid including isopropyl acrylate, stearyl methacrylate 2-ethyl hexyl acrylate; aromatic and alkyl aromatic esters of (meth)acrylic acid, (meth)acrylic acid esters of polyethylene glycol, polypropylene glycol, mixed polyethylene glycol/polypropylene glycol esters, and methyl and higher alkyl and aromatic ethers of these glycol (meth)acrylates, including polyethylene glycol (meth)acrylate and di-(meth)acrylate, polypropylene glycol(meth)acrylate and di-(meth)acrylate, polyethylene glycol co-poly propylene glycol(meth)acrylate and di-(meth)acrylate and methyl ethers thereof, and the (meth)acrylate esters of xe2x80x94OH terminated nonionic surfactants, and the corresponding maleate esters thereof. The poly(alkylene)glycols preferably have a molecular weight of from 200 to 5000, preferably from 200 to 1000.
Monomer C can be either an anionic, nonionic or cationic monoethylenically unsaturated monomer selected from one or more monoethylenically unsaturated monomers which are polymerizable with monomers A and B and are at least partially soluble in water or the reaction solvent, or in the other monomers if no water or solvent is used. Suitable monomers include one or more of the C3-C8 monoethylenically unsaturated carboxylic acids and their alkali metal and ammonium salts as used for monomer A; C1-C4 alkyl esters of acrylic acid and methacrylic acid such as methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), methyl methacrylate (MMA) and butyl methacrylate (BMA); C1-C4 hydroxyalkyl esters of acrylic acid and methacrylic acid such as hydroxyethlyacrylate (HEA), hydroxypropyl acrylate (HPA), and hydroxyethyl methacrylate (HEMA); acrylamide (Am), alkyl substituted acrylamides, such as methacrylamide (MAM), tert-butyl acrylamide (t-BAM) and N-tert-octyl acrylamide (t-OAM); styrene (Sty), sulfonated styrene (SS), sulfonated alkyl acrylamides, such as 2-acrylamidomethylpropanesulfonic (AMPS), vinyl sulfonates, allylsulfonic acid, methallylsulfonic acid, vinyl phosphonic acid, vinyl acetate, allyl alcohols, acrylonitrile, N-vinylpyrrolidone, acryloyl morpholine, N-vinylformamide, N-vinylimidazole, N-vinylpyridine; N,N-dimethylaminoethyl methacrylate (DMAEMA), N,N-dimethylaminoethyl acrylate (DMAEA), dialkyldimethyl ammonium chloride; [2-(methacryloloxy)ethyl]ammonium chloride, diallyldimethyl ammonium chloride (DADMAC), N-[3-(dimethylamino)propyl)acrylamide (DMAPA), N-[3-(dimethylamino)propyl)methacrylamide (DMAPMA) and (3-acrylamidopropyl)-trimethylammonium chloride (APTAC) and 2-(3-oxazolidinyl) ethyl methacrylate (OXEMA).
S and T are preferably derived from one or more initiator radicals, chain transfer agents or other groups which may be grafted onto the backbone via a radical reaction. S and T may be selected from one or more of H; OH; CH2R where R=H or C1 to C30 alkyl, cycloalkyl or alkylaromatic hydrocarbons; alcohols; ethers such as (CH2CH2O)rR where R is as defined above, and r is from 1 to 60; mixed poly(alkylene oxide) block copolymers such as (CH2CH2-O)s(CH2CH3CH2O)tR where R is as defined above, and s+t is from 2 to 60 or (CH2CH3CH2O)u(CH2CH2O)vR where R is as defined above, and u+v is from 2 to 60; sulphur or a sulphur containing groups such as, SR, SO2R, SO3H, SO4H and salts thereof in which R is as defined above; and N(H)R1 where R1=H or C1 to C15 alkyl.
D is selected from poly((C2-C4)alkylene)oxides or (C2-C4)alkylene)oxides monomers.
E is selected from C1-C50 alkyl, alkaryl and aralkyl groups. Preferably, E comprisesxe2x80x94linear or branched (C1-C24)alkyl, (C1-C24)alkaryl and (C1-C24)aralkyl groups, including but not limited to methyl, ethyl, butyl, n-octyl, dodecyl and stearyl, octylphenyl, nonylphenyl or dodecylphenyl, and benzyl or tolyl radicals. X is selected from groups such as acids, esters, amides, amines, nitrites, styrene and vinyl ethers.
The polymers of the present invention may be made by any suitable method, for example, by the methods described in U.S. Pat. Nos. 4,797,223, 4,404,309, 5,008,329 and 4,956,421, which methods are incorporated herein by reference.
It is contemplated that the polymer composition used in the method of the present invention will be made to contact the fabric in at least one of the following ways: i) by, for example, dabbing, dipping or spraying the fabric with a solution containing the polymer prior to soiling, this may be carried out as a fabric pre-use treatment operation to protect the surface of the fabric to prevent it from staining during use; ii) contacting the fabric with a solution of the polymer by, for example, dabbing, spraying or dipping prior to washing in a xe2x80x9cpre-spottingxe2x80x9d fabric treatment operation; iii) combining the polymer composition with the fabric detergent so that the polymer contacts the fabric using a xe2x80x9cthrough-the-washxe2x80x9d treatment process and iv) combining the polymer composition with a rinse added fabric softener through the rinse cycle of the washing operation.
The polymer composition used in the present invention may be used in solid form, such as a spray dried powder or granules, or in liquid form, preferably it will be used as an aqueous or co-solvent based solution.
The polymer composition may also contain crosslinkers to build polymer molecular weight and to produce modified polymer structures/conformations. These may include materials such as methylene bisacrylamide, pentaerythritol, di-, tri- and tetraacrylates, divinylbenzene, polyethylene glycol diacrylates and bisphenol A diacrylates.
The polymers of the present invention can be used in their present (acidic) form or neutralized to form salts containing carboxylate anions. Preferred alkali metal ions typically include sodium or potassium, alkaline earth metal cations such as magnesium and calcium, ammonium or tetra-alkyl ammonium salts, such as tetramethylammonium, or organic amine salts, such as the salts of tri-C1-C4 alkylamines, hydroxyethylamines, or the mono-, di- or tri-C1-C4-alkanolamines, or mixtures thereof.
As well as promoting the release of oily soil from fabrics, particularly cotton and cotton-containing fabrics, the present invention also provides the advantage in that it reduces fabric dinginess, that is, the dullness observed in respect of fabric which has endured repeated wash cycles. In a preferred embodiment of the present invention, the polymer composition is also effective at promoting the release of clay soil from fabrics, especially cotton and cotton-containing fabrics.
The invention will now be described with reference to the following examples. By way of example, certain hydrophobically modified polymers of the present invention may be prepared according to Examples 1-6 below: